CN102226028A - Self-cleaning antibacterial beta-crystal form PP-R cold-hot water pipe material and preparation method thereof - Google Patents
Self-cleaning antibacterial beta-crystal form PP-R cold-hot water pipe material and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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Abstract
The invention relates to a self-cleaning antibacterial beta-crystal form PP-R cold-hot water pipe material. The preparation method comprises the following steps of mixing calcium stearate and lanthana, adding pimelic acid into the mixture to cause a reaction, then adding nano-calcium carbonate into the reaction products obtained from the previous step and stirring uniformly to obtain a composite beta-crystal form nucleating agent, mixing orderly PP-R4220 resin, white oil 10, the composite beta-crystal form nucleating agent and anti-oxidants to produce a mixture, feeding the mixture into a parallel double screw extruder to produce beta PP-R resin particles, adding a silver ion salt and a zinc ion salt into nano-titanium dioxide, then mixing the nano-titanium dioxide, the beta PP-R resin particles and poly propylene wax to form a mixture, feeding the mixture into a parallel double screw extruder to produce a composite antibacterial mother material, and mixing uniformly the beta PP-R resin particles, the composite antibacterial mother material, poly propylene wax, methyl phenyl silicone oil and ultra -fine talc powder to form a mixture, feeding the mixture into an extruder or an injection machine to produce a self-cleaning antibacterial beta-crystal form PP-R cold-hot water pipe material. The material has the advantages of high usage temperature of 95 DEG C, high compressive strength, high thermal deformation temperature, high Vicat softening point, good self-clean performance and antibacterial effects.
Description
Technical field
The present invention relates to a kind of macromolecular material polypropylene cold and hot water tubing and preparation method thereof, the antibiosis and self-cleaning beta crystal β PP-R cold and hot water tubing that makes is mainly used in less than in 100 ℃ of heating, heat supply, the household drinking water plumber journey.
Background technology
Polypropylene random copolymer pipe is the PPR pipe, mainly as supplying pipe, is used for the cold and hot water supply system of buildings, comprises central heating system; Heating system in the buildings, comprise floor, wallboard and panel type heating system; Occasions such as purified water supply system capable of direct drinking, tubing such as galvanized pipe, pvc pipe, aluminum-plastic laminated tube, copper pipe and stainless steel tube have stronger advantage relatively, are the main products of existing market.But PPR tubing self exists shortcoming, mainly contains high thermal resistance, and the resistance to pressure difference is a little, and the long term operation temperature can not be above 70 ℃; After the PPR plastic water pipe used for some time, the inside pipe wall secondary pollution was serious, is the ground of growing of bacterium, legionella, became new human health killer and potential life and threatened, and was unfit to do the domestic running water pipe.The nontoxic salubrity requirement of PPR plastics tubing itself, but the PPR plastics tubing does not have self-cleaning function and kills the bacterium function, under this specific environment of domestic water, the backward technology of contaminated water source, waterworks and pipe network thereof outmoded unreasonable, make the PPR running water pipe of family expenses become the gathering ground and the bacterial growth ground of water pollution once again thing, the serious threat HUMAN HEALTH, a Chinese part city inhabitant statement-of-health in recent years discloses: rolling up of various diseases is relevant with household tap water water quality, and be relevant with the wrong choice supplying pipe.In addition, it is countless that the PPR running water pipe flows out the total plate count of water quality, and detect legionella pneumophilia 1 type, 5 types, startling more than the quantity, surpasses the galvanized pipe that has banned use of.Relevant department to the result of laboratory test of water quality is: reach 28 kinds of bacteriums and 16 kinds of metallic elements, wherein iron, manganese, zinc, lead, mercury exceed standard seriously.As seen after the PPR water pipe uses for some time, easily sheltering evil people and countenance evil practices, is the prolific hotbed of bacterium.
In order to overcome the use shortcoming of above conventional P PR water pipe, the present invention has prepared a kind of novel self-cleaning antibacterial beta crystal atactic copolymerized polypropene (β PPR) cold and hot water tubing, this product adopts the self-control composite beta crystal-type nucleater, complex antimicrobials, utilize the advanced person's of company pipe production line, prepared environment-friendly novel tubing of new generation.This product and PPR product are compared and mainly contained following advantage: 1, product has possessed the self-cleaning antibacterial function, can kill in the life-time service process attached to the bacterium on the tube wall; 2, can use in greater than the heating of 70 ℃ high temperature, heating system; 3, compressive strength height, long service life, safer, anti-ring stress ratio PP-R is high by 30%; 4, heat-drawn wire height, high temperature creep-resisting, resistance to elevated temperatures is good, and use temperature is than the high 25-30 of PP-R ℃; 5, thermal expansivity is little, is 1/6 of PP-R, installs and uses indeformablely, and outward appearance is beautiful.
Summary of the invention
The objective of the invention is the shortcoming at present common PPR water pipe: resistance to elevated temperatures, resistance to pressure are poor in the life-time service process, can not use in high temperature heating, Heat Supply Engineering, and work-ing life is short, do not have self-cleaning and shortcoming such as antibacterial.The invention provides a kind of beta crystal atactic copolymerized polypropene cold and hot water tubing that possesses antibiotic, self-cleaning function and preparation method thereof.
For realizing above purpose, technical solution of the present invention is: a kind of preparation method of antibiosis and self-cleaning beta crystal PP-R cold and hot water tubing may further comprise the steps:
The first step: the preparation of composite beta crystal-type nucleater: lanthanum trioxide, pimelic acid are joined in the reactor, under 55-65 ℃ of condition isothermal reaction 8-15 minute, be warming up to 105-115 ℃ then and continue reaction 1.5-2.5 hour, be cooled to room temperature; Material is entered in the mixing machine, add calcium stearate and pimelic acid, reaction is 3-5 minute under 20-30 ℃ and 200-300 rev/min of condition of mixing machine rotating speed; Add nano-calcium carbonate then, mixed 2-3 minute, obtain composite beta crystal-type nucleater; The consumption weight ratio of used calcium stearate, lanthanum trioxide and pimelic acid is 5-10:5-10:10-20;
Second step: the preparation of β PP-R resin raw material: get PP-R4220 resin or R503 resin earlier and add in the high-speed mixer, add No. 10 white oils down and mixed 1-2 minute 400-600 rev/min of high-speed mixer rotating speed, add composite beta crystal-type nucleater, antioxidant 1010 and oxidation inhibitor DSTDP mixing 1.5-2.5 minute then, then the material that mixes is entered parallel double-screw extruder, melt extrude, die face cutting under water, particle dehydration back oven dry is prepared into β PP-R resin raw material particle; The consumption weight ratio of used PP-R4220 resin or R503 resin, beta crystal-type nucleater, antioxidant 1010, oxidation inhibitor DSTDP and No. 10 white oils is 80-100:1-2:0.2-0.3:0.2-0.3:0.03-0.05;
The 3rd step: the preparation of composite antibiosis masterbatch: zine ion salt and silver ions salt adding dissolved in distilled water are obtained back zine ion salt and silver ions salt brine solution, zine ion salt and silver ions salt brine solution are joined in the nano titanium oxide, stirred 3-5 minute, leave standstill, water dashes, filter and drying is prepared into complex antimicrobials; Complex antimicrobials, Poly Propylene Wax and β PP-R resin raw material particle are joined in the high-speed mixer, enter parallel double-screw extruder after under 400-600 rev/min of high-speed mixer rotating speed, mixing, melt extrude, under water die face cutting, particle dehydration back oven dry obtains the composite antibiosis masterbatch; The consumption weight ratio of silver ions salt, zine ion salt, nano titanium oxide, β PP-R resin raw material particle and Poly Propylene Wax is 3-12:3-12:76-94:200-230:4-6;
The 4th step: the preparation of antibiosis and self-cleaning beta crystal PP-R cold and hot water tubing: earlier β PP-R resin raw material particle is joined in the mixing machine, add methyl phenyl silicone oil under the 200-300 rev/min of condition, mix and add superfine talcum powder, Poly Propylene Wax and composite antibiosis masterbatch after 1-2 minute successively, mix after 2-3 minute entering forcing machine or injection moulding machine then under 200-300 rev/min of condition, make antibiosis and self-cleaning beta crystal PP-R cold and hot water tubing; The consumption weight ratio of β PP-R resin raw material particle, composite antibiosis masterbatch, Poly Propylene Wax, methyl phenyl silicone oil, superfine talcum powder is: 80-100:2.5-3:0.3-0.4:0.2-0.3:0.5-1.
The working temperature of parallel double-screw extruder is in described second step: 175 ± 5 ℃ in a district, 215 ± 5 ℃ in two districts, 225 ± 5 ℃ in three districts, 225 ± 5 ℃ in four districts, 205 ± 5 ℃ in five districts;
The working temperature of parallel double-screw extruder is in described the 3rd step: 185 ± 5 ℃ in a district, 205 ± 5 ℃ in two districts, 215 ± 5 ℃ in three districts, 225 ± 5 ℃ in four districts, 205 ± 5 ℃ in five districts;
The working temperature of single screw extrusion machine is in described the 4th step: 190 ± 5 ℃ in a district, 200 ± 5 ℃ in two districts, 210 ± 5 ℃ in three districts, 220 ± 5 ℃ in four districts, 220 ± 5 ℃ in five districts, 210 ± 5 ℃;
The working temperature of described the 4th step pipe fitting injection moulding machine is: 190 ± 5 ℃ in a district, 210 ± 5 ℃ in two districts, 220 ± 5 ℃ in three districts, 210 ± 5 ℃ in four districts.
The fineness of described superfine talcum powder is the 3000-3500 order.
The sticking equal molecular-weight average of described Poly Propylene Wax is 10000-12000.
Described zine ion salt is zinc nitrate or zinc sulfate, and silver ions salt is Silver Nitrate or Sulfuric acid disilver salt.
The concentration of described zine ion salt and silver ions salt brine solution is 3-12kg zine ion salt/L and 3-12kg silver ions salt/L.
Nano titanium oxide in described the 3rd step is the nano titanium oxide after 200 ℃ of following preheating and dryings were handled in 1 hour.
The present invention also provides the antibiosis and self-cleaning beta crystal PP-R cold and hot water that is made by above-mentioned preparation method tubing.
Compared with prior art, beneficial effect of the present invention is:
1, because the present invention adopts homemade composite beta crystal-type nucleater, prepared the beta crystal Co-polypropylene, compare with traditional alpha-crystal form Co-polypropylene, beta crystal Co-polypropylene room temperature and low temperature impact strength are better, the heat-drawn wire height, resistance to elevated temperatures improves, and shows high toughness and ductility under high-speed stretch, be difficult for embrittlement, the pipe material inner wall ultra-smooth is difficult for hiding characteristics such as dirt.Because the distinctive performance advantage of beta crystal Co-polypropylene, thus tubing and pipe fitting can do thinner, material uses still less.Product can use the medium special use occasion of engineering in high temperature heating, heat supply.
2, because the present invention has adopted homemade composite antibiosis masterbatch, make tubing possess antibiosis and self-cleaning functions, make tubing in the process of life-time service, possess the function of kill bacteria, enable to satisfy for a long time the hygienic standard of tap water, can life-time service in the drinking-water pipe engineering.
3, the contrast of test of raw material of the present invention and end properties and common PP-R is as follows:
Common PP-R tubing and antibiosis and self-cleaning beta PP-R pipe over-all properties comparison sheet of the present invention:
(annotate: the antibacterial plastic concentrate addition is 2.4%)
Common PP-R raw material and antibiosis and self-cleaning β PP-R material performance comparison sheet of the present invention:
(annotate: the antibacterial plastic concentrate addition is 2.4%)
The performance index of antibiosis and self-cleaning beta PP-R pipe of the present invention such as following table:
(annotate: the antibacterial plastic concentrate addition is 2.4%)
The anti-microbial property test of antibiosis and self-cleaning beta PP-R pipe of the present invention
(annotate: the antibacterial plastic concentrate addition is 2.4%)
As can be seen from the above table, this tubing has good antimicrobial property to causing several typical bacteria that people infect such as intestines Escherichia, streptococcus aureus, and its antibiotic rate is all greater than 99%.Tubing is through after soaking 16h in 50 ℃ of hot water, and antibiotic rate slightly descends, but all greater than 99%.The anti-microbial property test data is provided by Guangdong Province's microbiological analysis inspection center.
Antibiosis and self-cleaning beta PP-R pipe hygienic safety performance of the present invention is tested as following table:
(annotate: the antibacterial plastic concentrate addition is 2.4%)
Meet the relevant health test of country from the hygienic safety performance of last table antibiosis and self-cleaning beta PP-R pipe.
Sanitary inspection office of test result Hubei Province Department of Public Health provides.
Embodiment
The present invention is further detailed explanation below in conjunction with embodiment
A kind of preparation method of antibiosis and self-cleaning beta crystal PP-R hot water pipe pipe, this preparation method may further comprise the steps successively:
The first step: the preparation of composite beta crystal-type nucleater: get the 5-10Kg lanthanum trioxide earlier, the 5-10Kg pimelic acid joins in the reactor, under 55-65 ℃ of condition isothermal reaction 8-15 minute, be warming up to 105-115 ℃ then and continue reaction 1.5-2.5 hour, be cooled to room temperature; Material is entered in the mixing machine, add 5-10Kg calcium stearate and 5-10Kg pimelic acid, 3-5 minute generating structure formula of reaction is La under 20-30 ℃ and 200-300 rev/min of condition of mixing machine rotating speed
3+Ca
2+[OOC (CH2)
5COO] material, add the 10-20Kg nano-calcium carbonate then, mixed 2-3 minute, obtaining structural formula is CaCO
3/ La
3+Ca
2+[OOC (CH2)
5COO] composite beta crystal-type nucleater.
Second step: the preparation of β PP-R resin raw material: PP-R4220 resin or the R503 resin of getting 80-100Kg earlier add in the high-speed mixer, add No. 10 white oils of 30-50g down and mixed 1-2 minute 400-600 rev/min of high-speed mixer rotating speed, add 1 – 2Kg composite beta crystal-type nucleater, 200-300g antioxidant 1010 and 200-300g oxidation inhibitor DSTDP mixing 1.5-2.5 minute then, then the material that mixes is entered parallel double-screw extruder, melt extrude, die face cutting under water, particle dehydration back oven dry is prepared into β PP-R resin raw material particle.
The 3rd step: the preparation of composite antibiosis masterbatch: 3-12Kg zine ion salt and 3-12Kg silver ions salt added dissolving obtains back zine ion salt and silver ions salt brine solution in the container that fills 500 ml distilled waters, zine ion salt and silver ions salt brine solution are joined in the 76-94Kg nano titanium oxide, stirred 3-5 minute, and left standstill to guarantee Zn
2+, Ag
+Fully be adsorbed on the porous nano titanium dioxide powder particles, the water flushing is to neutral again, and filtration and drying are prepared into complex antimicrobials; 85-118Kg complex antimicrobials, 4-6Kg Poly Propylene Wax and 200-230Kg β PP-R resin raw material particle are joined in the high-speed mixer, enter parallel double-screw extruder after under 400-600 rev/min of high-speed mixer rotating speed, mixing, melt extrude, die face cutting under water, particle dehydration back oven dry obtains the composite antibiosis masterbatch.
The 4th step: the preparation of antibiosis and self-cleaning beta crystal PP-R cold and hot water tubing: earlier 80-100Kg β PP-R resin raw material particle is joined in the mixing machine, add the 0.2-0.3Kg methyl phenyl silicone oil under the 200-300 rev/min of condition, mix and add 0.5-1Kg superfine talcum powder, 0.3-0.4Kg Poly Propylene Wax and 2.5-3Kg composite antibiosis masterbatch after 1-2 minute successively, mix after 2-3 minute entering forcing machine or injection moulding machine then under 200-300 rev/min of condition, make antibiosis and self-cleaning beta crystal PP-R cold and hot water tubing.
The working temperature of parallel double-screw extruder is in described second step: 175 ± 5 ℃ in a district, 215 ± 5 ℃ in two districts, 225 ± 5 ℃ in three districts, 225 ± 5 ℃ in four districts, 205 ± 5 ℃ in five districts;
The working temperature of parallel double-screw extruder is in described the 3rd step: 185 ± 5 ℃ in a district, 205 ± 5 ℃ in two districts, 215 ± 5 ℃ in three districts, 225 ± 5 ℃ in four districts, 205 ± 5 ℃ in five districts;
The working temperature of single screw extrusion machine is in described the 4th step: 190 ± 5 ℃ in a district, 200 ± 5 ℃ in two districts, 210 ± 5 ℃ in three districts, 220 ± 5 ℃ in four districts, 220 ± 5 ℃ in five districts, 210 ± 5 ℃;
The working temperature of described the 4th step pipe fitting injection moulding machine is: 190 ± 5 ℃ in a district, 210 ± 5 ℃ in two districts, 220 ± 5 ℃ in three districts, 210 ± 5 ℃ in four districts.
The fineness of described superfine talcum powder is the 3000-3500 order.
The sticking equal molecular-weight average of described Poly Propylene Wax is 10000-12000.
Described zine ion salt is zinc nitrate, and silver ions salt is Silver Nitrate.
The concentration of described zine ion salt and silver ions salt brine solution is 3-12kg zine ion salt/L and 3-12kg silver ions salt/L.
Nano titanium oxide in described the 3rd step is the nano titanium oxide after 200 ℃ of following preheating and dryings were handled in 1 hour.
Several principle of the present invention is described as follows:
1, the effect of main raw material(s) of the present invention:
Nano titanium oxide: porous support, sterilant;
Silver Nitrate: silver ions salt, sterilant; (Ag
+), big shape crystallization of water white transparency or white little crystallization;
Zinc nitrate: zine ion salt, sterilant; (Zn
2+), colourless crystallization;
Nanoporous lime carbonate: white powder, porous support, nucleator;
Lanthanum trioxide: white powder, nucleator;
Calcium stearate: white powder, nucleator;
Pimelic acid: nucleator (white monoclinic crystal);
Antioxidant 1010, oxidation inhibitor DSTDP: white powder prevents that product is aging in generation and use;
Poly Propylene Wax: lubricant;
White oil: lubricant;
Methyl phenyl silicone oil: releasing agent, smoothing agent makes the pipe material inner wall ultra-smooth;
Superfine talcum powder: adhesive agent makes methyl phenyl silicone oil stick to β PP-R resin raw material particle surface;
PP-R4220: random copolymerization polypropylene pipe raw material, Yanshan Petrochemical product, material resin;
R503: the random copolymerization polypropylene pipe raw material, raise sub-petroleum chemicals, material resin.
2, the purpose of adding white oil is moistening the PP-R4220 particle surface, and antioxidant 1010 and oxidation inhibitor DSTDP are sticked to the PP-R4220 particle surface uniformly; Adding talcous effect is to coat the methyl phenyl silicone oil β PP-R resin raw material particle that mixes.
3, select nano titanium oxide for use: being because nano titanium oxide is the environment-protecting asepsis raw material, itself is sterilant, again as carrier, and absorption silver ions and zine ion.
Embodiment 1: a kind of preparation method of antibiosis and self-cleaning beta crystal PP-R cold and hot water tubing, and this preparation method may further comprise the steps successively:
The first step: the preparation of composite beta crystal-type nucleater: get the 5Kg lanthanum trioxide earlier, the 5Kg pimelic acid joins in the reactor, isothermal reaction is 10 minutes under 60 ℃ of conditions, is warming up to 110 ℃ then and continues reaction 2 hours, is cooled to room temperature; Material is entered in the mixing machine, add 5Kg calcium stearate, 5Kg pimelic acid, 200-300 rev/min of mixing machine rotating speed, mixing temperature 20-30 ℃, to mix 3-5 minute, the generating structure formula is La
3+Ca
2+[OOC (CH2)
5COO] material, add the 10Kg nano-calcium carbonate then, mixed 2-3 minute, be prepared into composite beta crystal-type nucleater, structural formula is CaCO
3/ La
3+Ca
2+[OOC (CH2)
5COO].
Second step: the preparation of β PP-R resin raw material: PP-R4220 resin (the atactic copolymerized polypropene resin of Beijing Yanshan Petrochemical), the beta crystal-type nucleater for preparing of 1Kg, 200g antioxidant 1010 (white powder), the 200g oxidation inhibitor DSTDP(white granular thing of getting 80Kg earlier), 50g10 white oil (colourless transparent oil liquid).Earlier the PP-R4220 resin is joined in the high-speed mixer (rotating speed 400-600 rev/min), start mixing machine, the 30g10 white oil is slowly poured into, mixed 1 minute, and added beta crystal-type nucleater, oxidation inhibitor mixing 2 minutes then, then the material that mixes is entered parallel double-screw extruder, melt extrude, die face cutting is dried after the particle dehydration under water, is prepared into β PP-R resin raw material particle.
The working temperature of parallel double-screw extruder is: 175 ℃ in a district, 215 ℃ in two districts, 225 ℃ in three districts, 225 ℃ in four districts, 205 ℃ in five districts.
The 3rd step: the preparation of composite antibiosis masterbatch: 3Kg zinc nitrate, the adding of 3Kg Silver Nitrate are filled in the container of 500 ml distilled waters, stirred 3 minutes, make fully dissolving in distilled water.76Kg nano porous titanium dioxide (source?) 200 ℃ of following preheating and dryings 1 hour, be cooled to room temperature then.The zine ion that stirs, anion salt solution are poured in the high-speed mixer (rotating speed 400-600 rev/min) that the dried porous nano titanium dioxide of 76Kg is housed, mixed 3-5 minute, mixture is left standstill 2 hours then, to guarantee Zn
2+, Ag
+Fully be adsorbed on the porous nano titanium dioxide powder particles.The water flushing is filtered to neutral again, and it is standby to be prepared into complex antimicrobials after the drying.The 85Kg complex antimicrobials for preparing, 4Kg Poly Propylene Wax, 200Kg β PP-R resin raw material particle, join in the high-speed mixer (rotating speed 400-600 rev/min), enter parallel double-screw extruder after mixing, melt extrude, die face cutting under water, particle dehydration back oven dry obtains the composite antibiosis masterbatch.
The working temperature of parallel double-screw extruder is: 185 ℃ in a district, 205 ℃ in two districts, 215 ℃ in three districts, 225 ℃ in four districts, 205 ℃ in five districts.
The 4th step: the preparation of antibiosis and self-cleaning beta crystal atactic copolymerized polypropene (β PPR) hot water pipe pipe: get the β PP-R resin raw material that 80Kg prepares earlier, 2.5Kg composite antibiosis masterbatch, 0.3Kg Poly Propylene Wax, 0.2Kg methyl phenyl silicone oil, 0.5Kg superfine talcum powder (3500 order) joins in the high-speed mixer, thorough mixing, the material that mixes enters forcing machine and injection moulding machine, carries out the production of tubing and pipe fitting.
Technology controlling and process: earlier the β PP-R resin raw material particle for preparing is joined high-speed mixer, start low speed, rotating speed 200-300 rev/min, add methyl phenyl silicone oil then, mix and add superfine talcum powder (3500 order), Poly Propylene Wax after 1 minute successively, the composite antibiosis masterbatch, mixed then 2 minutes, the material that mixes enters forcing machine and injection moulding machine, carries out the production of tubing and pipe fitting.
The working temperature of described forcing machine is: 190 ℃ in a district, 200 ℃ in two districts, 210 ℃ in three districts, 220 ℃ in four districts, 220 ℃ in five districts, 210 ℃;
The working temperature of described injection moulding machine is: 190 ℃ in a district, 210 ℃ in two districts, 220 ℃ in three districts, 210 ℃ in four districts.
Embodiment 2:
With embodiment 1, asynchronously be: get the 10Kg lanthanum trioxide earlier, the 10Kg pimelic acid joins in the reactor, adds 10Kg calcium stearate, 10Kg pimelic acid again, adds the 20Kg nano-calcium carbonate then; Second step: the beta crystal-type nucleater for preparing of the PP-R4220 of 100Kg, 2Kg, 300g antioxidant 1010,300g oxidation inhibitor DSTDP, 50g10 white oil; The 3rd step: 12Kg zinc nitrate, 12Kg Silver Nitrate.The 94Kg nano porous titanium dioxide.The 118Kg complex antimicrobials for preparing, 6Kg Poly Propylene Wax, 230Kg β PP-R resin raw material particle; The 4th step: 100Kg β PP-R resin raw material, 3Kg composite antibiosis masterbatch, 0.4Kg Poly Propylene Wax, 0.3Kg methyl phenyl silicone oil, 1Kg superfine talcum powder.
Embodiment 3:
With embodiment 1, different is in second step: PP-R4220 is changed into R503.
Embodiment 4:
With embodiment 2, different is in second step: PP-R4220 is changed into R503.
Embodiment 5:
With embodiment 1, different was second step: the beta crystal-type nucleater for preparing of 1.5Kg.
Embodiment 6:
With embodiment 2, different was second step: the beta crystal-type nucleater for preparing of 1.5Kg.
Embodiment 7:
With embodiment 3, different was second step: the beta crystal-type nucleater for preparing of 1.5Kg.
Embodiment 8:
With embodiment 4, different was second step: the beta crystal-type nucleater for preparing of 1.5Kg.
Embodiment 9:
With embodiment 1, different was the 3rd step: zinc sulfate is replaced zinc nitrate.
Embodiment 10:
With embodiment 1, different was the 3rd step: Sulfuric acid disilver salt is replaced Silver Nitrate.
By the maximum operation (service) temperature of the antibiosis and self-cleaning beta crystal PP-R cold and hot water tubing of technical scheme of the present invention and embodiment preparation up to 95 ℃, compressive strength, heat-drawn wire, Vicat softening point are all higher, have self-cleaning function and antibacterial effect (referring to the subordinate list content of beneficial effect 3 parts of the present invention) preferably.
Claims (8)
1. the preparation method of an antibiosis and self-cleaning beta crystal PP-R cold and hot water tubing may further comprise the steps:
The first step: the preparation of composite beta crystal-type nucleater: lanthanum trioxide, pimelic acid are joined in the reactor, under 55-65 ℃ of condition isothermal reaction 8-15 minute, be warming up to 105-115 ℃ then and continue reaction 1.5-2.5 hour, be cooled to room temperature; Material is entered in the mixing machine, add calcium stearate and pimelic acid, reaction is 3-5 minute under 20-30 ℃ and 200-300 rev/min of condition of mixing machine rotating speed; Add nano-calcium carbonate then, mixed 2-3 minute, obtain composite beta crystal-type nucleater; The consumption weight ratio of used calcium stearate, lanthanum trioxide and pimelic acid is 5-10:5-10:10-20;
Second step: the preparation of β PP-R resin raw material: get PP-R4220 resin or R503 resin earlier and add in the high-speed mixer, add No. 10 white oils down and mixed 1-2 minute 400-600 rev/min of high-speed mixer rotating speed, add composite beta crystal-type nucleater, antioxidant 1010 and oxidation inhibitor DSTDP mixing 1.5-2.5 minute then, then the material that mixes is entered parallel double-screw extruder, melt extrude, die face cutting under water, particle dehydration back oven dry is prepared into β PP-R resin raw material particle; The consumption weight ratio of used PP-R4220 resin or R503 resin, beta crystal-type nucleater, antioxidant 1010, oxidation inhibitor DSTDP and No. 10 white oils is 80-100:1-2:0.2-0.3:0.2-0.3:0.03-0.05;
The 3rd step: the preparation of composite antibiosis masterbatch: zine ion salt and silver ions salt adding dissolved in distilled water are obtained back zine ion salt and silver ions salt brine solution, zine ion salt and silver ions salt brine solution are joined in the nano titanium oxide, stirred 3-5 minute, leave standstill, water dashes, filter and drying is prepared into complex antimicrobials; Complex antimicrobials, Poly Propylene Wax and β PP-R resin raw material particle are joined in the high-speed mixer, enter parallel double-screw extruder after under 400-600 rev/min of high-speed mixer rotating speed, mixing, melt extrude, under water die face cutting, particle dehydration back oven dry obtains the composite antibiosis masterbatch; The consumption weight ratio of silver ions salt, zine ion salt, nano titanium oxide, β PP-R resin raw material particle and Poly Propylene Wax is 3-12:3-12:76-94:200-230:4-6;
The 4th step: the preparation of antibiosis and self-cleaning beta crystal PP-R cold and hot water tubing: earlier β PP-R resin raw material particle is joined in the mixing machine, add methyl phenyl silicone oil under the 200-300 rev/min of condition, mix and add superfine talcum powder, Poly Propylene Wax and composite antibiosis masterbatch after 1-2 minute successively, mix after 2-3 minute entering forcing machine or injection moulding machine then under 200-300 rev/min of condition, make antibiosis and self-cleaning beta crystal PP-R cold and hot water tubing; The consumption weight ratio of β PP-R resin raw material particle, composite antibiosis masterbatch, Poly Propylene Wax, methyl phenyl silicone oil, superfine talcum powder is: 80-100:2.5-3:0.3-0.4:0.2-0.3:0.5-1.
2. preparation method according to claim 1 is characterized in that:
The working temperature of parallel double-screw extruder is in described second step: 175 ± 5 ℃ in a district, 215 ± 5 ℃ in two districts, 225 ± 5 ℃ in three districts, 225 ± 5 ℃ in four districts, 205 ± 5 ℃ in five districts;
The working temperature of parallel double-screw extruder is in described the 3rd step: 185 ± 5 ℃ in a district, 205 ± 5 ℃ in two districts, 215 ± 5 ℃ in three districts, 225 ± 5 ℃ in four districts, 205 ± 5 ℃ in five districts;
The working temperature of single screw extrusion machine is in described the 4th step: 190 ± 5 ℃ in a district, 200 ± 5 ℃ in two districts, 210 ± 5 ℃ in three districts, 220 ± 5 ℃ in four districts, 220 ± 5 ℃ in five districts, 210 ± 5 ℃;
The working temperature of described the 4th step pipe fitting injection moulding machine is: 190 ± 5 ℃ in a district, 210 ± 5 ℃ in two districts, 220 ± 5 ℃ in three districts, 210 ± 5 ℃ in four districts.
3. preparation method according to claim 1 and 2 is characterized in that: the fineness of described superfine talcum powder is the 3000-3500 order.
4. preparation method according to claim 1 and 2 is characterized in that: the viscosity-average molecular weight of described Poly Propylene Wax is 10000-12000.
5. preparation method according to claim 1 and 2 is characterized in that: described zine ion salt is zinc nitrate or zinc sulfate, and silver ions salt is Silver Nitrate or Sulfuric acid disilver salt.
6. preparation method according to claim 1 and 2 is characterized in that: the concentration of described zine ion salt and silver ions salt brine solution is 3-12kg zine ion salt/L and 3-12kg silver ions salt/L.
7. preparation method according to claim 1 and 2 is characterized in that: the nano titanium oxide in described the 3rd step is the nano titanium oxide after 200 ℃ of following preheating and dryings were handled in 1 hour.
8. the antibiosis and self-cleaning beta crystal PP-R cold and hot water tubing that makes by claim 1 or 2 described preparation methods.
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| CN102720896A (en) * | 2012-06-11 | 2012-10-10 | 杭州恒标管业有限公司 | Pipe as well as preparation method and purpose of pipe |
| CN103383023A (en) * | 2013-07-29 | 2013-11-06 | 刘忠斌 | Antibiosis polypropylene random (PPR) drinking water pipe |
| CN103421247A (en) * | 2013-01-10 | 2013-12-04 | 上海上丰集团有限公司 | Polypropylene random copolymer (PP-R) composite material, nano anti-bacterial pipe and preparation method of PP-R composite material and nano anti-bacterial pipe |
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| CN103421247B (en) * | 2013-01-10 | 2015-08-19 | 上海上丰集团有限公司 | PP-R composite material, nano-antibacterial pipe and preparation method thereof |
| CN103383023A (en) * | 2013-07-29 | 2013-11-06 | 刘忠斌 | Antibiosis polypropylene random (PPR) drinking water pipe |
| CN103589063A (en) * | 2013-10-31 | 2014-02-19 | 安徽工贸职业技术学院 | High-temperature resistant antibacterial plastic |
| CN105150487A (en) * | 2015-08-14 | 2015-12-16 | 浙江伟星新型建材股份有限公司 | Fractional crystallization method for Beta-form-crystal PPR pipe extrusion |
| CN105150487B (en) * | 2015-08-14 | 2017-11-17 | 浙江伟星新型建材股份有限公司 | A kind of fractional crystallization method of beta crystal PPR pipe extrusion |
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| CN108410067A (en) * | 2017-10-30 | 2018-08-17 | 成都川盛塑胶有限公司 | A kind of hot and cold water compound plastic pipe with antibacterial functions |
| CN110406065A (en) * | 2018-04-28 | 2019-11-05 | 上海伟星新型建材有限公司 | A kind of β-PPR pipe and its processing method |
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| CN111657343A (en) * | 2020-05-22 | 2020-09-15 | 湖北恒大包装有限公司 | Fruit and vegetable fresh-keeping corrugated carton and preparation method thereof |
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